Dialkylamino disazo sulfonic acid dyestuffs

ABSTRACT

DYESTUFFS OF THE FORMULA   ((A1-)(M-O-SO2-)-PHENYL)-N=N-(2-B2,5-B1-1,4-PHENYLENE)-   N=N-(R-1,4-PHENYLENE)-N(-R1)-R2   IN WHICH A1 IS HYDROGEN, ALKYL, ALKOXY, HALO OR TRIFLUOROMETHYL, B1 AND B2 ARE EACH HYDROGEN, LOWER ALKOXY, LOWER ALKYL, CHLORO OR BROMO, M IS HYDROGEN, ALKALI METAL OR NH4+, R IS HYDROGEN, ALKYL, ALKOXY, TRIFLUOROMETHYL, CHLORO, BROMO OR FLUORO, AND R1 AND R2 ARE EACH ALKYL, HYDROXYALKYL, CYANOALKYL, LOWER ARALKYL OR SUBSTITUTED LOWER ARALKYL. THE DYES HAVE A GOOD AFFINITY FOR NATURAL AND SYNTHETIC POLYAMIDE FIBERS AND SHOW GOOD LIGHT FASTNESS, SOLUBILITY, WASS AND PERSPIRATION FASTNESS AS WELL AS GOOD BARRE COVERAGE.

3,823,131 DIALKYLAMINO DISAZO SULFONIC A'CID DYESTUFFS Hans Alfred Stingl, Toms River, NJ., assignor to Toms River Chemical Corporation, Toms River, NJ. No Drawing. Filed June 23, 1971, Ser. No. 156,057 Int. Cl. C09b 31/04, 31/08; D06p 1/06 US. Cl. 260-186 7 Claims :ABS'IRACT 10F PIS-CLOSURE Dyestuffsjof the. formula H in which A is hydrogen, alkyl, alkoxy, halo or trifluoromethyl, B and B are each hydrogen, lower alkoxy, lower alkyl, chloro or bromo, M ishydrogen, alkali metal or NH.,+, R is hydrogen, alkyl, alkoxy, trifluoromethyl, chloro, bromo or fluoro', and R and R are each alkyl, hydroxyalkyl, cyanoalkyl, lower aralkyl or substituted lower aralkyl. The dyes have a good affinity for natural and synthetic polyamide fibers and'show gOOd light fastness, solubility, wash and perspiration fastness as well as good barr coverage.

' BACKGROUND 'O'F '""I=HE" INVENTION The dyestuffs of this invention are valuable for dyeing natural and synthetic polyamide fibers having good light fastness, wet fastness and barr coverage. In comparison with dyestuffs as described in British Pat. 1,198,886, the dyestuffs of this invention display better transfer and levelling characteristics. In comparison to dyestuffs disclosed in French Pat. 792,343, the present dyestuffs have a greater stability to hydrolysis.

SUMMARY OF THE INVENTION In accordance with this invention, new dyes have been discovered which have a good affinity for natural and synthetic polyamide fibers, including wool, silk and nylon. These compounds dye said fibers from neutral or acid aqueous dyebaths and show good light fastness, solubility, wash and perspiration fastness and barr coverage. In the more preferred dyes of this invention, the dyes possess these properties to a remarkable degree.

The invention is, therefore, concerned with dyestuffs, their application to polyamide fibers and to processes for their preparation.

The compounds of this invention may accordingly be represented by the following structural formula:

wherein each of A is hydrogen, C lower alkoxy (preferably C C C lower alkyl (preferably C trifiuoromethyl, chloro or bromo, B and B are each hydrogen, C lower alkoxy, C lwer alkyl, chloro, or bromo, R is hydrogen, C lower alkyl (preferably C C lower alkoxy (preferably C trifiuoromethyl,

- chloro, bromo or fluoro, R and R are each C hydroxyalkyl, C cyanoalkyl, C alkoxyalkyl, C chloro or bromo lower alkyl, C lower alkyl (preferably each of the alkyl moieties of the above groups contain 4 or less carbon atoms), phenyl-C lower alkyl or substituted phenyl-C lower alkyl, wherein the substituent on the phenyl moiety may be chloro, bromo, lower alkoxy or Patented July 9, 1974 lower alkyl of up to 4 carbon atoms (especially up to 2 carbon atoms) or cyano, and M is hydrogen, alkali metal (Na, K, Li) or NH In the more preferred aspect of this invention, A is hydrogen, methyl, methoxy or chloro, and especially in a position ortho todth azo group; B and B are each hydrogen, methyl or methoxy and preferably when methyl only one of B or B being methyl at any one time; R is hydrogen, methyl, methoxy or chloro; R and R are each C m hydroxyalkyl (especially C C cyanoalkyl (especially canoethyl), C alkyl (especially C or benzyl, and most preferred R is lower alkyl or hydroxyalkyl and R any of the above, especially cyanoethyl.

The dyestuffs of this invention can be prepared by wellknown methods in the art. For example, an appropriate sulfonated aromatic amine may be diazotized and coupled in the paraposition to another appropriate aromatic amine. The second amine may suitably be coupled in the form of its N-methane sulfonic acid and the product thereafter saponified to obtain the desired substituted para-aminoazobenzene compound. This compound is then diazotized by well-known means and reacted with an appropriate coupler of the formula Preferably, in carrying out the process for the preparation of the compounds of this invention, an aniline compound of the formula is: and the diazotized aniline compound described above are coupled under well-known coupling conditions to obtain an intermediate azo compound of the formula Alternatively, the unsulfonated compound (3) can b prepared in a manner similar to the above process, followed by sulfonation under well-known means to obtain compound (3). This intermediate azo compound may then be appropriately diazotized and subsequently coupled with a coupler of the formula Specific compounds of the formula (1) which may be mentioned are: metanilic acid, sulfanilic acid, 3-amino- 4methoxybenzenesulfonic acid, 3 amino-4-chlorobenzenesulfonic acid, 3-amino-4-propylbenzenesulfonic acid, 3-amino 4 propoxybenzenesulfonic acid, 3-amino-4- bromobenzenesulfonic acid, 4-amino-3-ethylbenzenesulfonic acid, 4-amino 3 methylbenzenesulfonic acid, 4- amino-3-ethoxybenzenesulfonic acid and 4-amino-3- chlorobenzenesulfonic acid.

Compounds of formula (2) which may be mentioned are: 2-methoxy-S-methylaniline, 2-ethyl-5-bromoaniline, 2- or 3-methylaniline, 2,5-dichloroaniline, 2,5-dimethoxyaniline, 2,5-dipropoxyaniline, 2,5-diethylaniline, 2-methoxyaniline, 2- or 3-ethylaniline, 2- or 3-chloroaniline and aniline.

Compounds of formula (4) which may be mentioned are:

N-cyanoethyl-N-ethylaniline, N-cyanoethyl-N-ethyl-m-toluidine, N-cyanoethyl-N-methylaniline, N-cyanoethyl-N-methyl-m-toluidine, N-cyanoethyl-N-butylaniline, N-hydroxyethyl-N-cyanoethyl aniline, N-hydroxyethyl-N-cyanoethyl-m-toluidine, N-hydroxyethyl-N-ethylaniline, N-hydroxyethyl-N-ethyl-m-toluidine, N-hydroxyethyl-N-methylaniline, N-hydroxyethyl-N-butylaniline,

N- (2) hydroxypropyl-N-ethylaniline,

N- (2 )hydroxypropyl-N-cyanoethylaniline, N,N-di (hydroxyethyl) aniline,

N,N-di hydroxyethyl m-toluidine, N,N-dihydroxyethyl -m-chloraniline, N,N-di (hydroxyethyl) -o-chloraniline, N,N-di (hydroxypropyl) -o-toluidine, N,N-di hydroxypropyl) -m-toluidine, N,N-di (hydroxyethyl -o-anisidine,

N,N-di hydroxyethyl) -m-anisidine, N-ethyl-N-chloroethylaniline, N,N-diethylaniline,

N-ethyl-N-b enzylaniline, N-ethyl-N-benzyl-m-toluidine,

N- 2) hydroxyethyl-N-b enzylaniline,

N- 2) cyanoethyl-N-benzylaniline, N-ethyl-N-b enzyl-o-anisidine,

N-benzyl-N- fi-cyanoethyl -3-methoxyaniline, N-b enzyl-N- ,B-hydroxybutyl) -3 -ethoxyaniline, N- (p-methylb enzyl) -N-propyl-2-ethylaniline, N,N-diethyl-3-chloroaniline, N,N-dipropyl-2-bromoaniline,

N- m-ethoxybenzyl) -N-butylaniline,

N- m-chlorob enzyl) -N-ethylaniline,

N- p-methoxyethylbenzyl) -N-ethylaniline, N- (p-cyanob enzyl) -N-ethylaniline, N,N-dibenzylaniline,

N- ethyl-N-methoxyethylaniline, N-methyl-N- 3 -chloropropyl) -aniline, N-propyl-N- (2-bromoethyl) aniline, N-benzyl-N-methoxyethylaniline,

N,N- di-fl-cyanoethyl) aniline, N-phenethyl-N-ethylaniline, and

N- (p-methoxyphenethyl) -N-ethylam'line.

The starting materials used to prepare the dyestuffs of the instant invention are known compounds and can readily be prepared by well-known means. For example, the compounds of formula (4) can be prepared by the action of an appropriate alkylating agent upon a ring substituted aniline compound at an elevated temperature and usually in the presence of an inorganic or organic acid binding agent. Similarly, a ring substituted N-monosubstituted aniline can be reacted with an alkylating agent as above to result in a compound of formula (4) in which R and R are different.

The compounds of this invention are particularly suitable for dyeing natural and synthetic polyamide fibers, especially nylon, giving dyed fabrics with good properties such as light fastness, wet fastness and barr coverage.

The fibers can readily be dyed or printed, for example, from aqueous dyebaths at pH values of 5.5 to 7.5 and preferably 6.0 to 7.0 at a liquor ratio of :1 to 40:1,

.4 although other liquor ratios can be employed. The initial pH can be adjusted to the desired value by an appropraite acid or basic treatment or by buffering the solution.

The following examples are given by way of illustration:

Example 1 (A) 20.8 parts by weight of 3-amino-4-chlorobenzenesulfonic acid are dissolved in parts of water and 4 parts of caustic soda. Ice, 20 parts of concentrated hydrochloric acid, and a solution of 7 parts of sodium nitrite in 20 parts of water are added to achieve diazotization at 37 C.

(B) 15.3 parts of 2,5-dimethoxyaniline, dissolved at 45 C. in 120 parts of water and 10 parts of concentrated hydrochloric acid, are combined with the diazotized 3- amino 4-chlorobenzenesulfonic acid and enough ice to keep the temperature below 7 C. and the pH is raised to 2 with 20% soda ash solution. The coupling product 2,5 dimethoxy 4-(2'-chloro-5'-sulfobenzeneazo)aniline is separated by filtration, washed with very dilute hydrochloric acid, and dried.

(C) This dried monoazo compound is charged into part of 12% nitrosyl sulfuric acid (in anhydrous sulfuric acid), held at 3035 C. overnight, and then poured slowly on 250 parts of ice and 20 parts of salt. The rediazotized compound is separated by filtration, reslurried in 800 parts of cold water, combined with a solution of 14 parts of N-B-cyanoethyl-N-ethylaniline in 14 parts of glacial acetic acid, and stirred at room temperature overnight. 4 parts by weight of salt per 100 parts of reaction volume are added and the product is separated by filtration. It is reslurried in 1800 parts of Water at 95 C., made slightly alkaline with soda ash, salted with 10 parts by Weight of salt per 100 parts of volume, cooled to 70 C., recovered by filtration, and dried. The compound has the structure When N-fi-hydroxyethyl-N-ethylaniline is used in place of N-B-cyanoethyl-N-ethylaniline in Example 1, a compound is obtained with the structure OCH:

/ C2Hs CzHA 0 H OaNa CH3 which dyes nylon in very even violet shades of similar characteristics.

Example 3 (A) 17.3 parts of metanilic acid are dissolved in 70 parts of water and 8 parts of 50% by weight caustic soda solution. Ice, 22 parts of concentrated hydrochloric acid, and a solution of 7 parts of sodium nitrite in 20 parts of water are added with sufiicient ice to maintain the temperature at 0-3 C. to diazotize the metanilic acid.

(B) 15.3 parts of 2,5-dimethoxyaniline, dissolved at 45 C. in parts of water and 11 parts of concentrated hydrochloric acid are combined with the diazotized metanilic acid, using suflicient ice to keep the temperature below 5 C. and the pH is raised to 2.5 with 20% soda ash solution. After completion of the coupling, the product is dissolved at pH 9 with 50% caustic soda solution and then salted with 50 parts of sodium chloride. Rediazotization is accomplished by addition of 7.5 parts of sodium nitrite, followed by an aqueous solution of 21 parts of naphthalenesulfonic acid and sufiicient sulfuric acid to establish a congo acid reaction. A temperature of 32 C. is maintained for 2 hours.

(C) This reaction mass is combined with a solution of 17 parts of N-B-cyanoethyl-N-ethylaniline in 17 parts of glacial acetic acid at 5 C. and the pH is raised to 4, then more slowly, during one hour, to 6 by the addition of a 25% aqueous soda ash solution. Stirring is continued overnight while the temperature is permitted to rise to 15 C.

The product is separated by filtration and washed with a 5% aqueous sodium chloride solution. It has the structure OCH:

8 OaNB CH and dyes nylon from weakly acid dyebaths in very even bluish red shades of good light and wash fastness.

CzHs

Example 4 OCH3 CH which dyes nylon from neutral dyebaths in very lightfast and washfast violet shades.

Example 5 (A) 17.3 parts of sulfanilic acid are diazotized in 50 parts of ice-water and 11 parts of concentrated hydrochloric acid by the rapid addition of a concentrated solution of 7 parts of sodium nitrite in water at about 4 C.

(B) The resulting diazotized sulfanilic acid is combined at a temperature below 5 C. with 13.7 parts of 2-mcthoxy-S-methylaniline previously dissolved in 120 parts of water at 45 C. and 11 parts of concentrated hydrochloric acid. Sufficient 20% soda ash solution is added to raise the pH to 3.0 and the mixture is stirred for a period of five hours.

(C) The mixture from B is combined with a solution of 17 parts of N-B-cyanoethyl-N-ethylaniline in 17 parts of glacial acetic acid at C. and the pH is raised to 3, then more gradually to 5 by the addition of a 25% aqueous soda ash solution. Stirring is continued overnight while the temperature is permitted to rise. Finally, some salt is added and the pH is reduced to ca. 1 with concentrated hydrochloric acid. The product is filtered off and washed with tenth normal hydrochloric acid. It is represented by the formula I and dyes nylon from neutral or weakly acid dyebaths in even red shades of good light fastness and wash fastness.

Example 6 When N-B-hydroxyethyl-N-ethylaniline is used in place of N-B-cyanoethyl-N-ethylaniline in Example 5, the compound formed is represented by the formula and dyes nylon from neutral dyebaths in very even very bluish red shades.

6 Example 7 (A) 17.3 parts of metanilic acid are diazotized employing the procedure set forth under Example 3 (A).

(B) The resulting diazotized metanilic acid is combined at a temperature below 5 C. with 13.7 parts of 2-methoxy-5-methylaniline previously dissolved in 120 parts of water at 45 C. and 11 parts of concentrated hydrochloric acid. Sufficient 20% soda ash solution is added to raise the pH to 3.0 and the mixture is stirred for a period of five hours.

After completion of the coupling, the product is filtered off, redissolved in 500 parts of water at 50 C. with 8 parts of sodium chloride after cooling to 20 C. Rediazotization is accomplished by addition of 7.2 parts of sodium nitrite, followed by an aqueous solution of 21 parts of naphthalenesulfonic acid and sufiicient sulfuric acid to establish a congo acid reaction. One hour later an amount of sodium chloride equivalent to 20% of the volume of the slurry is added and the slurry cooled to 8 C. The precipitate is collected by filtration.

(C) The precipitate from B is reslurried in 250 parts of ice water and combined with a mixture of 18 parts of N,N-di( 3-hydroxyethyl-)aniline, 120 parts of water, and 8 parts of concentrated sulfuric acid. 10 parts of sodium acetate are added, followed by 70 parts of lutidine, and stirring is continued at 25 C. overnight.

The product is precipitated from the wine red solution by acidification with concentrated hydrochloric acid, filtered, and washed with tenth normal hydrochloric acid. It has the structure CzlLOH l /C,H,

I C5H40H S 0311 CH:

Example 9 (A) 17.3 parts of metanilic acid are diazotized employing the procedure set forth under Example 3 (A).

(B) The pH of the resulting solution is adjusted to 2.5 by additionof sodium bicarbonate. 6.6 parts of sodium acetate is added, followed by the addition of 22.5 parts of o-anisidyl-N-methanesulfonic acid, while maintaining the temperature of the reaction mixture at about 57 C. by means of ice and cold water and stirring for a period of 1 hour. 38 parts of a 50% by weight solution of caustic soda are then added and the mass is heated at C. for 8 hours. The mass is then cooled, 28 parts of sodium bicarbonate are added to adjust the pH to 9, salted with 33 parts of sodium chloride and filtered.

The filter cake is dissolved in 800 parts of water at 30 C. To this solution there is added 7 parts of sodium nitrite, followed by addition of an aqueous solution of 21 parts of naphthalenesulfonic acid and suflicient sulfuric acid to establish a congo acid reaction and the mixture maintained at 32 C. for a period of 2 hours.

(C) The mixture from B is cooled to 10 C. and the pH is raised to ca. 3 with soda ash. A solution of 18 parts of N-B-cyanoethyl-N-ethyl-m-toluidine in 18 parts of glacial acetic acid is added over a period of 15 minutes, followed by enough soda ash solution in two hours to approach pH 5. Salt is added after completion of the reaction in the amount of parts by weight per 100 parts of reaction volume and the product is isolated by filtration. It has the structure SOxNa CH:

and dyes nylon from neutral or weakly acid dyebaths in very even red shades that possess very good light fastness and wash fastness.

Example Similarly, using N-fl-cyanoethyl-N-ethylaniline in place of N-B-cyanoethyl N ethyl-m-toluidine, and lutidine to promote the coupling, there is obtained a compound of the structure that dyes nylon in scarlet shades with otherwise similar characteristics as mentioned for the preceding compound.

The following examples illustrate further the scope of this invention. These compounds are prepared by following the procedure of the examples as set forth and employing the appropriate starting materials.

8 When the above-described preparations are carried out with potassium salts and caustic potash in place of sodium salts and caustic soda, the potassium salts of the corresponding dyestuffs are obtained.

Example 46 To obtain the dyes in the form of their free acids, an aqueous suspension of an instant dye is rendered strongly acid with a mineral acid, e.g. concentrated hydrochloric acid, or sulfuric acid and the insoluble acid form of the dye is separated by filtration.

The free acid form of the dye can be neutralized with other bases, as for example lithium hydroxide, lithium carbonate or ammonia, to .form dye salts containing the corresponding cations, as desired.

Example 47 m A: 0 B1 0 m I /R1 N=NN=N N R: m S03Na 0 B2 0 In Position Procedure of Numexample be! SO3Na A1 B1 B: R R1 R2 11 p H H H O-CHa C2H5 C2H4CN 12 m H H H C2H5 C2H4OH 13 m H H H O-CHa C2H5 CzH CN 14 m H H H C2H5 CzHqCN 15 m H OCH3 H 02H CzH4OH 16 m H OCH CH3 0-CH3 0 H CzHr CN 17 m O-OCH3 OCH3 CH3 H C H4OH C2H4OH 18 m O-OCHa OCH; CH H CaH5 C2H4 H 19 m O'OOHQ OCH3 OCH3 C2H5 C2H4OH 20 p O-Cl OCH3 OCH3 CzHs C2H4OH 21 p O-Cl OCH3 OCH; 0-CH3 CzHs CzH4CN 22 p O-C]. OCH3 OCH; O-CHz C H4OH C3H4OH 23 m H H H H CzH4OH p H H H H C2115 C2H CN p H H H H CZHQOH C2H4CN m H CH3 H H C H4OH gzHzcN m H CH3 H O-CHa CzHs 2H CN m H CH H H C2H4OH C2H OH m H OCH; H H CH3 CzH CN m H OC H O-CHa CzH4OH CzH CN p O-CHa OCHa H O-CHa C2H5 CzHrCN p H OCH3 CH3 O-CH3 C2H4OH CzHgOH m O-CHa OCH3 CH 0-CH3 2H5 C3H CN m H OCH; OCH; H CH3 C2H4CN p H 0 CH 0 CH O-CH; CzH5 CzH4CN m H OCH3 H H CHzCH-OHCH; CzHgCN 9 37 In H 00113 H m-Cl CZH4OH CzH OH 9 38 111 H OCH; H O-Cl C H4OH C H OH 9 u 39 D1 H OCH; H H CH:CHOHCH3 CHzCHOH-CH 3 40 m H OCHa OCHa H CH3 CH2- OCH;

3 J: 41 m H OCH: OCHg H CzH CN CzHr- 9 "7. 42 m H OCH: H H CzH5 CzH C1 9 ...i 43 m H OCH! H H C2115 C2H5 9 44 p H Bl H H C2H4OH C H OH 9 45 m H H 01 H CH3 CZH4OH The fabric is then removed from the bath, rinsed with cold water, and dried. It is dyed a very even and fast shade of bordeaux.

Example 48 The procedure of Example 47 is repeated with 0.2 parts of the dyestufr's described in Examples 2, 3, 4, and 11, respectively. One obtains very even and fast shades of violet to scarlet.

Example 49 Into an aqueous dyebath containing 4000 parts of Water, 0.05 to 0.5 parts of the dyestuffs described in Examples 5, 7, 18, 24, 25, 26, 29 and 34, respectively, 1 part of nonionic wetting agent, 10 parts of anhydrous sodium sulfate and 10 parts of acetic acid, 100 parts of nylon fabric are entered at 60 C. The temperature is raised to 96 C. in 45 minutes and held at 96 C. for one hour while the fabric is mildly agitated. The fabric is then removed from the bath, rinsed with cold water and dried. It is dyed very even and fast shades of reddish orange to bluish red.

Example 50 Similarly, when 0.05 parts of dyestuff from Example 5 and 0.05 parts of dyestuif from Example 7 are used in the above example, similar results are obtained.

What is claimed is:

1. Diazo dyestuff of the formula wherein each of A is hydrogen, C .;lower alkoxy, C -C lower alkyl, trifluoromethyl, chloro or bromo, B and B are each hydrogen, C lower alkoxy, C l0wer alkyl, chloro or bromo, R is hydrogen, C lower alkyl, C lower alkoxy, trifiuoromethyl, chloro, bromo or fluoro, R and R are each C hydrxyalkyl, C cyanoalkyl, C a1koxyalkyl, C chloro or bromo lower alkyl, C lower alkyl, phenyl-C lower alkyl or substituted phenyl- C lower alkyl, wherein the substituent on the phenyl moiety is chloro, bromo, lower alkoxy or lower alkyl of up to 6 carbon atoms or cyano, and M is hydrogen, alkali metal or NH 2. Disazo dyestuff of claim 1 wherein A is hydrogen, methyl, methoxy or chloro, B and B are each hydrogen, methyl or methoxy, only one of B or B being methyl at any one time, R is hydrogen, methyl, methoxy or chloro,

and R and R are each C hydroxyalkyl, C cyanoalkyl, C lower alkyl or benzyl.

3. Disazo dyestuff of claim 2 wherein R is C alky1 or C hydr0xya1kyl.

4. Disazo dyestulf of claim 2 wherein R is C alkyl and R is cyanoethyl.

5. A compound of claim 1 of the formula OCH;

I /C2Hs CQHQCN SOaNa 6. A compound of claim 1 of the formula OCH:

CzH5 Q Q N:N -N=N -N I CzH CN SOaNa OCH;

7. A compound according to claim 1 of the formula crncrnoN Q Q Q N=N N=N N I oHzorn SO3N8 References Cited UNITED STATES PATENTS 3,637,649 1/1972 Meininger et al 260191 3,092,616 6/1963 Gaetani 260186 3,096,140 7/1963 Gaetani 260174 X 3,222,355 12/1965 Gaetani 260186 3,293,240 12/1966 Koike et al. 260186 3,479,332 11/1969 Jirou et al. 260186 3,485,814 12/1969 Speck 260186 3,502,646 3/1970 Canonica et al. 260186 FOREIGN PATENTS 792,343 10/ 1935 France 260-186 OTHER REFERENCES Farbwerke Hoechst, Chemical Abstracts, volume 73, page 49, Article No. 121537w (1970).

FLOYD DALE HIGEL, Primary Examiner US. Cl. X.R. 

